Vat dyestuffs of the anthraquinone series



Patented Dec. 27, 1938 2 ldl 858 UNITED STATES ?ATENT OFFECE VATDYESTUFFS OF THE ANTHRAQUINONE SERIES Donald P. Graham, South Milwaukee,Wis., as-

signor to E. I. du Pont de Nemours & Company, Wilmington, DeL, acorporation of Delaware No Drawing. Application January 5, 1938, SerialNo. 183,457

2 Claims. (Cl. 260-274) This invention: relates to the preparation ofamino 4',8-dichloranthraquinone with two molnewvat dyestuffs of theanthraquinone series ecules of Bz-l-aminobenzanthrone, then hyand moreparticularly to the preparation of those drolyzing ofi the benzoylgroups in caustic aldyestuffs resulting from the caustic alkali fusionkali with simultaneous ring-closure of the acri- 5 of thedi(benzanthronyl-amino)-di(anthraquidine rings. The resulting diaminocompound is 5 nonylamino) anthraquinones of the following thencondensed" with two molecules of l-chlorogeneral O u anthraquinone andagain subjected to the caustic fusion. The isomeric product in which thetwo 0 benzanthronylamino radicals may be introduced in the 1 and 8positions may be prepared by sub- 10 0= =o stituting the 1,8dibenzoylamino-4,5dichloroanthraquinone as the starting material in thisprocess.

The following examples are given to illustrate the invention more-fully.The parts used are by weight.

Example 1 80 parts of 1,5di(benzoylamino) -4,8-dichloroanthraquinone areslurried in 800 parts of molten t, naphthalene'with 80 parts ofBz-l-aminobenzanthrone, 40 parts of soda ash, 5 parts of copper 2acetate and 0.5 part of copper powder. The charge is heated-to 212=to215 C. and held for 15 hours. It is then cooled to 170 C. anddiluted'with 1000 parts of o-dichlorobenzene, cooled where the carbonatoms 1, 2, 3; 4; X and Y comto 80 C., filtered, washed witho-dichlorobenpose onebenzenering of the center anthraquizene, followedby alcohol and then by Water, and none nucleus. dried. parts of this dryintermediate are 30 The invention has for its object thepreparadissolved in a melt consisting of 300 parts of KOH tion of newand valuable dyestuffs of the anand 350 parts of ethyl alcohol. The meltis thraquinone series which dye cotton in fast yelheated to 0., allowingsome alcohol to eslowish olive shades. The aluminum chloride fucape, andheld at 135 to C. for 2 hours. It sion product oftetra-alpha-anthraquinonylamiis then drowned in 2000 parts of cold waterand 35 noanthraquinone is known to give a dyestufi oxidized by theaddition of 10 parts of nitroben- 35 which dyes cotton in very greenishkhaki shades zene-meta-sodium sulfonate or by aeration. The of excellentfastness properties. Attempts have product is filtered off, washedalkali-free, and been made to obtain a dyestuff which would dye dried.23 parts of this intermediate are slurmuch yellower shades and stillexhibit the same ried in 300 parts of molten naphthalene with 19 40 goodfastness properties. I have now found that parts ofl-chloroanthraquinone, 20 parts of soda 40 by the substitution of twoBz-l-aminobenzanash, 2 parts of copper acetate, and 0.2 part of thronegroups for the two anthraquinonyl radicopper powder. The charge isheated to 212 to cals in either the 1,5- or 1,8-position of the cen- 215C. for 15 hours, cooled to 170 C., diluted ter anthraquinone nucleus ofthe pentaanthriwith 400 parts of o-dichlorobenzene, cooled to 80 45 mideand subsequent treatment with an alkaline C., filtered, Washed witho-dichlorobenzene, fol- 45 condensing agent that new and valuabledyelowed by alcohol and water and dried. stufis are obtained which dyecotton in extremely 15 parts of this dried product are dissolved inyellowish olive shades of good fastness. a melt comprising 225 parts ofKOl-I and 225 According to this invention the new dyestufi parts ofethyl alcohol, heated to C. (allow- 0 may be prepared by condensing1,5-dibenzoyling some alcohol to distill off) and refluxed at so 150 to155 C. for 1 hour. It is then drowned in 2000 parts of water, oxidizedwith 10 parts of nitrobenzene-meta-sodium sulfonate (or by aeration),and the crude color filtered off and dried.

The product is acid pasted by dissolving 1 part of the dry crude colorin parts of 93% H2804. This mass is drowned in water, filtered, washedacid free and dried or milled up as a smooth aqueous paste.

The product (when dried) is an olive to black solid dissolving in 95%H2304 with a violet color and dyeing cotton in fast yellow olive shadesfrom an olive colored vat.

' Example 2 If 1,8-di(benzoylamino) -4,5 dichloroanthraquinone issubstituted for 1,5-di(benzoylamino)- 4,8-dichloroanthraquinone as thestarting intermediate in the preceding example, an isomeric dyestuff isobtained which also gives a violet solution in 95% sulfuric acid and anolive vat. It dyes cotton in yellow-olive shades.

As an alternative procedure to that given in the specific example above,the condensation product of the1,5-dibenzoylamino-4,8-dichloroanthraquinone with the two moles ofBz-l-aminobenzanthrone may be hydrolyzed with sulfuric acid in place ofcaustic, and after the introduction of the two moles ofl-chloroanthraquinone the above product may be subjected to causticalkali fusion to effect a ring-closure. This procedure is found to givea product identical to that described in Example 1. This same proceduremay be employed in the preparation of the1,8-dibenzanthronylaminoanthraquinone compound. In all cases theresulting products dye cotton in bright yellow-olive shades of goodfastness properties.

While it is generally believed that the alkaline condensation of thedibenzanthronylaminoanthraquinone eifects the ring-closure of theanthrimide group to the acridine through the 2 position of benzanthronemolecule, it has not been definitely established that ring-closure ofthe two anthraquinonylaminoanthraquinone groups takes place, althoughthis is believed to be the case for apparently some type of ring-closureis effected. It has not been definitely determined however whether anacridine or a carbazole ring is formed, or whether both anthrimidegroups are converted to heterocyclic rings.

I claim:

1. The dyestuffs resulting from the caustic alkali condensation of theproducts of the following general formula Where the carbon atoms 1, 2,3, 4, X and Y compose one benzene ring of the center anthraquinonenucleus, which dye cotton in yellow-olive shades of good fastnessproperties.

2. The dyestuif resulting from the caustic alkali condensation of theproduct of the following formula which dyes cotton in yellow-oliveshades of good fastness properties.

DONALD P. GRAHAM.

Certificate of Correction Patent No. 2,141,858. December 27, 1938.DONALD P. GRAHAM It is hereby certified that errors appear in theprinted specification of the above numbered patent requ1r1ng correotlonas follows: Page 2, second column, lines 4 to 22 inclusive, claim 1,strlke out the formula and insert instead the following:

and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 21st day of February, A. D. 1939.

[SEAL] Henry Van Arsdale. Acting Commissioner of Patents.

